Polymethine dyestuffs and a process of preparing them



Patented Apr. 13, 1937 in I if 2,077,063

.oF BBEPARINGTHEM Raul Wolff. Frankfort-onetheaMain, Germany, assignor to General Aniline Works,'1nc., New

,YorlgN. Y., a corporatiorggifbelawgrg a No Drawing. Application December 1,934 Serial N In FPlQflXP9Wb9EJ1L6a The present invention relates to polymethine y stu s and to; a roc ss of pr p in hem- I have foundj that valuable dyestufis of the polymethine seriesmay beobtained by condens- 5 ing an indoline compound which 'contalns'in alpha-positionito the nitrogen a reactive methylene group in which one hydro en atom is replaced by the aldehyde group, for instance, an

aldehydeof the followinggeneral formula:

wherein X means a substituent, with an equimoleoular proportion of a partially hydrogenated heterocyclic nitrogen compound such as, 90 for instance, dihydro-u-phenylindol, tetrahydroquinoline or the like, in the presence of a condensing agent such as, phosphorus oxychloride, piperidine, or acetic anhydride, and advantageously in presence of a solvent such benzene, acetic anhydride, nitrobenzene, pyridine or the like. The products thus obtained are new. Products of the following constitution are, for instance, obtained:

CH: CH:

C. to 20 C, and this temperature is maintained until the formation of the dyestuff is completed.

50 The benzene is expelled, and the remaining dyestufi is dissolved in hot water; on cooling it separates from the solution in the form of well defined crystals. It dyes tannin mordanted cotton yellow tints of an excellent clearness and 55 very good fastness to light.

9 Claims. (01. 2604*.8

(2) 20.1 parts of 1 3,3 trimethylindoline zw mti yls ezaidehyde condensed with 13-3 parts of (IllhYClIO-oc-I'IIGthYliIldOl in the manner beg i i Examp e and e od c is worked up as therein described. A dyestuff is obtained which also dyes tannin mordanted cotton yellow tints of the same clearness and good fastness to light.

(3) 20.1 parts of 1,3 3:trimethylindoline-2- methylene-w-aldehyde are condensed with 13.3 parts of tetrahydroquinoline in 100 grams of benzene at about C'. in the presence of 6 parts of phospho u xychlorideen e is then expelled and the dyestuft' so" obtained is crys allize rqm Waist T y ta liz d. dyestufiidyes tannin mordanted cotton clear'y'ellow tints of very good fastness to light.

(4) 23 parts of 1,3,3-trimethyl-5-methoxyindoline-2-methylene-waldehyde are condensed with 13.3 parts of tetrahydroquinoline in the manner described in the foregoing examples in the presence of 6 parts of phosphorus oxychloride. A dyestuff is obtained which crystallizes from water in the form of small needles of a golden luster. It dyes tannin mordanted cotton bright yellow tints of an excellent fastness to light.

We claim: I claim: aldehyde compound of the general formula:

on. on, x

wherein X means a member of the group consisting .of hydrogen and methoxy with a hydrogenated heterocyclic nitrogen compound of the group consisting of dihydro-indoles and tetrahydroquinolines by means of a condensing agent of the group consisting of phosphorus oxychloride and acetic anhydride in the presence of a solvent.

3. The process which comprises condensing at a temperature of about 15 C. to about 20 C. 1,3,3 trimethylindoline-2-methylene-w-a1dehyde with (iihYdIO-a-DhEHYIiI'ldOl by means of phosphorus oxychloride in the presence of benzene.

4. The process which comprises condensing at atemperature of about 15C. to about 20 C. 1,3,3- trimethylindoline-2-methylene-w-aldehyde with dihydro-a-methylindol by means of phosphorus oxychloride in the presence of benzene.

5. The process which comprises condensing at a temperature of about 15 C. to about 20 C. 1,3,3- trimethyl-5-methoxyindoline 2 -methylene-w-aldehyde with tetrahydroquinoline by means of phosphorus oxychloride in the presence of benzene.

6. The compounds of the general formula:

wherein X means a member of the group consisting of hydrogen and methoxy and R means the radical of a hydrogenated heterocyclic compound of the group consisting of dihydro-indoles and tetrahydroquinolines.

7. The compound. of the formula:

CH: C1

H oam dyeing tanned cotton yellow tints of an excellent clearness and very good fastness to light.

8. The compound of the formula:

lent clearness and good fastness to light.

9. The compound of the formula:

dyeing tanned cotton bright yellow tints of an excellent fastness to light.

PAUL WOLFF.

Patent No. 2,077,065.

CERTIFICATE OF CORRECTION April 15, 1957.

PAUL woLFF.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 1, second column, line 28, strike out the words and colon "we Ola-1mg" ;line 50 before aldehyde insert as line 1 of the claim the numeral and words 1. The process which comprises condensing an; and that the said Letters Patent should be read with these corrections therein that the same may conform to the record oi the case in the Patent Office.

Signed and sealed this 16th day of November, A. D. 1957.

. I Henry Van Arsdale, (Seal) Acting Commissioner of Patents. 

